Reducing fog in reversal color films processed in developers containing couplers



United States Patent Office 3,113,864 Patented Dec. 10, 1963 Jersey NoDrawing. Filed June 11, 1959, Ser. No. 819,539 14 Claims. (Cl. 96-22)This invention relates to color photography, and more particularly, to amethod of processing multi-layer color films or papers in such a manneras to reduce color fog and give maximum color density.

In multi-layer photographic elements used for color photography, thereare usually three selectively sensitive emulsion layers coated on oneside of a single support. F or example, the uppermost layer is generallyblue-sensitive, the next layer is generally green-sensitive, while theemulsion layer adjacent the support is generally redsensitive. Betweenthe blue-sensitive and green-sensitive layers is a filter layer forabsorbing blue radiation which may be transmitted through theblue-sensitive layer. The multilayer coating can also have otherinterlayers for specialized purposes. Such multilayer materials havebeen previously described in the prior art, such as Mannes et al. US.Patent 2,252,718, issued August 19, 1941. Other arrangements of thesensitive layers are also known.

Color materials of the type employed in the instant invention are thoseintended primarily for reversal processes, wherein the exposed materialis given a conventional black-and-White development, followed by areversal exposure, or exposures, and color development.

Our invention is particularly useful in processing reversal colormaterials, wherein the color-forming components or couplers areincorporated in the color developers.

It is, therefore, an object of our invention to provide an improvedmethod of inhibiting color fog and increasing the maximum color densityof reversal color materials intended for processing in color developerscontaining color-forming materials or couplers. Another object is toprovide a method of inhibiting color development fog in the variouslayers of multilayer color materials. Other objects will become apparentfrom a consideration of the following description and examples.

During the black-'and-white development of multilayer color materials,fog centers are introduced into the unexposed regions, and uponselective reversal re-exposure and subsequent color development, theseunexposed areas have deposited therein coupled color-forming materials,resulting in severe loss of color quality. This loss of color quality isparticularly severe in the processing of red-sensitized photographicsilver halide emulsions, which are processed in a reversal colordeveloper containing the coupling material, resulting in the developmentof cyan fog in the blue-andagreen sensitive layers. This fog isparticularly severe in emulsions which contain any of the known chemicalsensitizing agents, such as gold sensitizers, sulfur sensitizers, etc.,or polyethyleneglycol type sensitizers.

We have discovered a new method for eliminating or substantiallyreducing the formation of color fog in the unexposed layers ofmultilayer color materials intended for reversal processing in a colordeveloper containing the color-forming materials \or couplers. Thismethod consists in contacting the multilayer color material afternegative development in the black-and-white developer, but before colordevelopment, with an aqueous solution containing certain benzothiazoliumor naphthathiazolium salts. This treatment allows normal colordevelopment to take place in the exposed layer, but inhibits thedevelopment of undesired fog in the unexposed layers.

Of course, the reversal process used in the present invention is onewhich has been previously described in the prior art, and it is to beunderstood that our invention resides in a modification of this priorart technique. That is, it is known that in reversal processing, acolored image can be formed by adding to certain color developingsolutions, a compound which couples during development with theoxidation product of the developing agent, thus forming a coloredcompound which is deposited adjacent to the developed silver halidegrains or the silver image, during such color development. The colordensity improving treatment employed in our invention is applied to themultilayer color material after conventional negative development in ablack-and-white developer, and before or after one of the reversalre-exposures for the differentially sensitize demulsion layers. Themultilayer color material is, of course, given successive colordevelopment treatments for each of the differentially sensitizedemulsion layers after reversal reexposure for each emulsion layer. Thecompounds employed in conjunction with the color developing agents andwhich couple with the oxidation products of the developing agents duringdevelopment are generally referred .to as colorforming compounds, orcouplers. Such compounds usually belong to one :of three widely knowntypes, i.e., pyrazolone couplers, phenol couplers, and open-chainketomethylene couplers. These couplers produce, respectively, magenta,cyan and yellow' images.

The quaternary salts useful in practicing our invention comprisecompounds represented by the following general formula:

BIT-X I z) 11 wherein R represents a hydrogen atom or a lower alkylgroup, such as methyl, ethyl, etc. (e.g., an .alkyl group containingfrom 1-2 carbon atoms), R represents a hydrogen atom, an aryl group(e.g., phenyl, 0-, mand p-tolyl, o-, mand p-methoxyphenyl, etc), or anarylenethiazolyl group (e.g., Z-benzothiazolyl, 3-benzothiazolyl, 2 (,3naphthothiazolyl) etc.) D represents the nonmetallic atoms necessary tocomplete an aromatic nucleus (e.g., benzene, naphtholene, etc., as wellas their substitution products, including such members substituted bymethyl, ethyl, methoxyl, ethoxyl, etc.), m represents a positive integerof from 1-26 (provided that n represents a positive integer of only fromabout l-3 when R, represents an aryl group) and X represents an acidradical, such as perchlorate, bromide, benzenesulfonate,toluenesulfonate, methyl sulfate, ethyl sulfate, etc.

A particularly useful group 'of quaternary salts em; braced by Formula Iabove includes the compounds represented by Ithe following generalformula:

wherein R, D and X each have the values given above, and m represents apositive integer of from about 126.

Typical quaternary salts embraced by Formula I above include thefollowing:

wHz) 10 N Decamethylene-bis-benzothiazolium perchlorate C2115 O S Oz-CsH4-C H3 (p) 3 ethylbenzothiazolium-p-toluenesulfonate (n) C aHis O SO2C sH4-C a (p) 3hexylbenzothiaZ01ium-p-toluenesulfonate 3-(Z-benzothiazolylmethyl benzothiazolium-p-toluenesulfonate3-nonylbenzothiazolium-p-toluenesulfonate C-CHs HsC-C N l Br OHZCH2CHATrimethylcne-bis-2-methy1benzothiazolium bromide C-CHa I s0,0 0HT-0 3(2-benzothiaz0lylmethyl) -2-methylbenzothiazolium-p toluenesulfonateZ-methyl-fl-naphthothiazolium metho-p-toluenesu1f0nate Ethylenebis-benzothiazolium bromide OH HO N C H4) 5Pentamcthylene-bis-benzothiazolium perchlorateHexamethylene-bis-benzothiazolinm perchlorate 01 C H4-C 5H53-benzylbenzothiazolium chloride S\CH I-ICNonamethy1enebis-benzothiazolium perchlorate \CH HO/ 010 4 C10 4Hexacosane-1,ZG-bis-benzothiazolium perchlorate Many of these quaternarycompounds have been previously described in the prior art. For example,the his compounds represented by Formula II can be prepared according tothe methods described in Wilson US. Patent 2,425,774, issued August 19,1947, as well as by the method described by Allen and Wilson US. Patent2,694,716, issued November 16, 1954. Such methods generally comprise thefusion of a heterocyclic base with an alkylene halide. Such techniquesare Well known to those skilled in the art. Alkyl esters of organicsulfonic acids can also be fused with thiazole bases to provide thesalts of our invention.

The cycloammonium salts useful in practicing our invention are employedin the form of their aqueous solutions. The amount of quaternary saltused in the solutions can be varied, depending upon the particularemulsions employed, the concentration of silver halides in theemulsions, etc. In general, we have found that concentrations of fromabout 0.25 to 1.0 gram per liter of solution are particularly eifective.However, the most advantageous concentration for a particular colormaterial can be determined by running a series of test strips of silverhalide emulsions through a reversal color process of the type describedherein, the concentration of the quaternary salt in the treatingsolution being varied. The multilayer color materials treated in ourinvention can be immersed in the treating solution, or for continuousprocesses, the treating solution may be applied, for example, by meansof rollers, etc. In general, it has been found desirable to give themultilayer color material a short washing treatment after treatment withthe quaternary salt in order to avoid spotting.

The treatment of the multilayer color materials of our invention can bemade either before or after the reversal re-exposure step. However, itmust be made after the negative development in the black-and-whitedeveloper, but before development in the color developer. We have foundthat the beneficial effects of the quaternary salts of our inventioncannot be obtained if these materials are incorporated in the emulsions.In some instances, the thiazolium salt (e.g., Compound 11a) can beincorporated in the color developing solution where it is soluble insuch solution.

The advantages of our invention have been obtained in a large number ofmultilayer color materials and the effect is not dependent upon anyparticular emulsions or developing compositions. The elfects have beenfound to be outstanding when the red-sensitive layer is color developedfirst in that the development fog centers present in the blue and greenlayers, which were not re-exposed after black-and-white development, donot develop spontaneously to form unwanted cyan dye and the resultantloss of color quality in these layers. However, the effects areapparent, though not as outstanding when the photographic silver halideemulsion layers intended for the production of magenta or yellow imagesare color developed first. Typical couplers for use in the colordevelopers of our invention comprise the following:

COUPLERS FOR USE IN COLOR DEVELOPERS Cyan Couplers l5-benzenesulfonaminol -naphthol (2)2,4-dichloro-5-benzenesulfonamino-1-naphthol (3 2,4dichloro-5-(p-toluenesulfonamino l-naphthol (4) 5-( 1,2,3,4-tetrahydronaphthalene-6-sulfonamino l-naphthol (5 2,4-dichloro-5-(4-bromodiphenyl-4-sulfonamino l-naphthol (6) o-,B-Naphthalenesulfonamino) -1-naphthol (7) 5- (m-nitrobenzenesulfonamino-1-naphthol (8) 5-(quinoline-5-sulfonamino) -1-naphthol (U.S.

2,3 62,59 8 (9 2-acetylamino-5 -methylphenol l) 2-benZoylamino-3 ,5-dimethylphenol l 1 2-u- (p-tert. amylphenoxy-n-butyrylamino--methylphenol 12) 2-11- (p-tert. amylphenoxy)-n-butyrylamino-4-chloro S-methylphenol 13 2- (p'-tert.amylphenoXy-p-benzoyl) amino-4-chloro- 5 -methylphenol 14) 2- 4-tert.amyl-3'phenoxybenzoylamino) -3,5-dimethyl- 1 -phenol l5)2-phenylacetylamino-4-chloro-5-m.ethylphenol 16)2-benzoylamino-4-ch1oro-S-methylphenol 17)2-anilinoacetylarnino-4-chloro-5-methylphenol 18) 2-{4- [oc-(4"-t61t.amylphenoxy) -n-butyrylamino] benzoylamino}-4-chloro-5-methylphenol (251-pheny13 -acetylamino-5-pyrazolone 26) 1-pheny1-3-propionylamino-S-pyrazolone (27)l-phenyl-3-dichloroacetylamino-5 -pyrazo1one (28)l-phenyl-3-benzoylamino-S-pyrazolone (29 1-pheny1-3 (m-arninobenzoyl)-amino-5 -pyrazolone hydrochloride 3 0) 1 -pl1enyl-3 diamylbenzoyl)amino-S-pyrazolone (3 l 1-phenyl-3-phenylcarbamylamino-5-pyrazolone (32)1-phenyl-3-phenoxyacetylamine-5-pyrazolone (3 31-phenyl-3-p-aminobenzoylamino-S-pyrazolone (34) l-phenyl-3-(o-carboxybenzoyl) amino-S-pyrazolone (3 51-phenyl-3-palmitylamino-S-pyrazolone (3 6) 1-phenyl-3- (p-sec.amylbenzenesulfonylamino -5- pyrazolone (37) l-phenyl-3- [p- (p'-sec.amylbenzoyl) aminobenzoylamino] -5 -pyr azolone (3 8) 1-m-tolyl-3- [m-,B-phenylpropionyl aminobenzoylamino] -5-pyrazolone (3 9) 1-m-tolyl-32,4-di-tert. butyl-m-tolyloxyacetyl amino) -5-pyrazolone (40) 1- [p-(p'-te1't. butylphenoxy) phenyl] -3- [p- (benzoylamino) -benzoylamino1-5-pyrazolone (41 1- (p.-tert. butylphenoxyphenyl -3(p-n-amyloxybenzoylamino -5-pyrazolone (42) 1- [p- (p'-tert.butylphenoxy) phenyl] -3- 3 ,S-di-methoxyb enzoyl) amino-S-pyrazolone(43 1- [p- (p'-tert. butylphenoxy) phenyl] -3- [m-(p-toluenesulfonylamino benzoylamino] -5-pyrazo1one (44) 1- [p-( 3,5-dimethylphenoxy) phenyl] -3- (4-n-amyloxy-3 -methylbenzoylamir1o -5-pyrazolone (45 3 (p-nitrophenoxyacetylamino) l- (2,4,6-trichlorophenyl-5 -pyraz olone Yellow Couplers (46) pw-Benzoylacetaminobenzenesulfonamide (47 pw-Benzoylacetamino) benzenesulfon-N-methylamide(48) pw-Benzoylacetamino) benzenesulfonanilide (49)4-benzenesulfonamino-w-benzoylacetanilide (50) 4- (p-toluenesulfonamino)-w-benzoylacetanilide (51) 4- (p-laurylbenzenesulfonamino-w-benzoylacetanilide (5 2) 1,4-di- [p- (benzoylacetamino)benzenesu'lfonamino 1 benzene 5 3 N,N-di-(p-benzoylacetaminophenyl)benzene-1,3-

disulfonamide (5 4) N- (p-benzoylacetaminophenyl) -4-[pbenzoylacetamino) -benzenesu1fonamido] benzenesulfonamide (5 5N4-benzoylacetyl-N- (2-benzothiazolyl sulfanilamide (56p-Acetoacetaminobenzenesulfon-[i-naphthalide (5 7p-Furoylacetaminobenzenesulfon-N-cyclohexylamide 5 8) p-(4-ethoxybenzoylacetamino) benzenesulfonamide (59) Terephthaloyl-bisl(p-N-amylsulfonamide) acetanilide] (60) p-Quinoline-8sulfonamino-w-benzoylacetanilide (61p-Acetoacetamino-o-methylbenzenesulfon-N-anilide (62)N,N-di-(p-benzoylacetaminophenol naphthalene- 1,5-disulfonamide ('63 p-(Benzenesulfonamino benzoylacetone (64) N-benzoylaceto-o-anisidine Thecolor-forming developers useful in our invention have been previouslydescribed in the prior art, and our invention is not to be restricted tothe use of any particular color-forming developer. Particularly usefulcolor-forming developers comprise those containing primary aromaticamines, containing an amino (substituted or not) or hydroxylsubstituent. Phenylenediamines and substituted derivatives thereofcontaining a primary amino group have been found to provide particularlyuseful results. Typical of such color-forming developers are thesulfonamido substituted p-phenylenediamines disclosed in Weissberger US.Patent 2,548,574, issued April 10, 1951, the substitutedp-phenylenediamines disclosed in Weissberger et a1. U.S. Patent2,566,271, issued August 28, 1951. Of course, other phenylenediaminecolor-forming developers can be employed with equal facility in theprocess of our invention.

The first, or negative, developer employed in the process of ourinvention is generally a rapid developer of the MQ type, i.e., acombination of hydroquinone and Elon (p-N-methylaminophenol) developer,although other high-speed developers, such as those containing Phenidonecan also be employed.

The following examples will serve to illustrate more fully the manner ofpracticing our invention.

EXAMPLE 1 A portion of a red-sensitized, gelatino-silver-bromiodideemulsion which had been sensitized with a sulfur compound, a goldcompound and a small amount of the oleyl ether of a polyethyleneglycolhaving a molecular weight of about 900 was coated on a cellulose acetatefilm support. The coating was then dried and exposed to a step table forsecond, using a 500-Watt, 3000 K. light source, filtered with a WrattenNo. 29 Filter (i.e., a filter transmitting only light from about 610 to700 millimicrons) and a 0.8 neutral density filter, on an Eastman TypeIb Sensitometer. The exposed coating was then developed for minutes in adeveloper having the following composition:

Grams Elon developing agent 2.0 Sodium sulfite, desiccated 90.0Hydroquinone 8.0 Sodium carbonate, monohydrated 52.5 Potassium bromide5.0

Cold water to make 1.0 liter.

The coating was washed for 2 minutes with water.

The coating was then given a reversal re-exposure seconds flash) with aNo. 2 Photofiood Filter with a Lowry red Filter No. 92, set at adistance of about one meter. The coating was developed to an adequateD-max. for minutes in a developer having the following composition:

Sulfuric acid' (conc.) cc 1.5 Sodium hexametaphosphate g 0.5 Sodiumsulfite (anhydrous) g 5.0 Color developer 1 g 0.6 Sodium carbonate(monohydrate) g 15.0 Potassium bromide g 0.25 Potassium iodide (0.1%solution) cc 2 Coupler 2 g 1.2 Sodium hydroxide g 0.3 Carbowax 1540 g1.0 Water to make one liter.

1 -amino-3-methyl-N,N-diethylaniline hydrochloride.

1 2,4dich1oro-5- (p-toluenesulfonamido) -1-naphth01.

The coating was washed for 10 minutes in water and immersed for 2minutes in a silver bleach bath having the following composition:

G. Potassium ferricyanide 100 Potassium bromide 10 Borax a 7.5 Boricacid 5.0

Water to make one liter.

G. Sodium thiosulfate (pentahydrate) 200 Sodium sulfite (anhydrous) 10Water to make one liter.

The coating was then washed in water for 10 minutes and dried. In orderto obtain a measure of the cyan fog, an identical strip of coating wasput through the same process, except that the flash re-exposure wasomitted.

Additional strips of the same coating were put through the same processexcept that the strips were treated for 2 minutes in an aqueous solutioncontaining Compound 1 above, after red re-exposure, but before colordevelopment. After treatment in this pre-bath, the strips were washedfor 2 minutes in water. The treating solution was obtained by dissolving1.0 g. of Compound 1 in 175 cc. of methyl alcohol and diluting thesolution to 1 liter with water. The D-max. and cyan fog for each ofthese coatings was measured, the following results being obtained:

Compound No. Cyan D-Max. Cyan Fog Control (none) 3. 32 0.52 1 (1.0g./1iter) 3. 56 0.23

EXAMPLE 2 In a manner similar to that described above, a multilayercolor material was processed both with and without the pre-bathtreatment in an aqueous solution containing Compound 1 above (i.e.,decamethylene-bisbenzothiazolium perchlorate). The multilayer colormaterial comprised a conventional cellulose acetate film support havingcoated thereon in order, a gelatin layer, ,a red-sensitized silverhalide emulsion layer, a greensensitized silver halide emulsion, ayellow filter layer comprising Carey Lea silver, and a blue-sensitivesilver halide emulsion layer. Each of the silver halide emulsion layerswas gold and sulfur sensitized as in Example 1, and each contained asmall amount of a polyethylene glycol sensitizer having a molecularweight of about 900.

Processing of the strips of coating was exactly as described in Example1 above, except that the blackand-White development was for 12 minutes,instead of 10, and 0.50 gram of H-acid was added to the color,

developer. The following results were obtained:

Compound No. Relative Speed Cyan D-Max. Cyan Fog The speeds were read ata density of 0.3 below maximum density.

EXAMPLE 3 A portion of a blue-sensitive, gelatino-silver-bromiodideemulsion which had been sensitized with a sulfur compound, a goldcompound and a polyethyleneglycol sensitizer having a molecular weightof about 900 was coated onto a cellulose acetate support. The coatingwas then dried and cut into several strips. One strip of the coating wasexposed to a step table for A second to a SOO-Watt, 3000 K. lightsource, filtered with a Wratten No. 49 Filter (i.e., a filtertransmitting only light of wavelengths between about 400 and 510millimicrons) on an Eastman Type Ib Sensitometer. The exposed strip wasdeveloped for 10 minutes in a hydroquinone-Elon Developer of the typeused in Example 1, and washed for 2 minutes in water.

The strip was given a reversal re-exposure for about 15 seconds (flash)with a No. 2 Photoflood set at a distance of about 1 meter.

The strip was then developed for minutes in a color developer having thefollowing composition:

The strip was then washed, bleached, fixed and washed exactly asdescribed in Example 1 above. In order to determine fog, a duplicatestrip was processed, except that the reversal r e-exposure with thePhotoflood was omitted.

In a manner described immediately above, duplicate strips were processedto a yellow image, except that the strips were bathed for 2 minutes inan aqueous solution containing decamethylene-bis-benzothiazoliumperchlorate (1.0 g./ liter), followed by a 2-minute wash after reversalre-exposure, but before color development. The results obtained were asfollows:

Compound No. Yellow D-Max. I Yellow Fog Control l. 82 0. 64 1 (1.0g./liter) 1. 52 0. 30

EXAMPLE 4 In exactly the manner described in Example 2 above (i.e., with12 minutes black-and-white development and with color developercontaining 0.5 g. of H-acid), strips of the multilayer color materialdescribed in Example 2 were processed, both with and without treatmentin one of the pre-baiths containing a quaternary salt. The bromiodideemulsions were sulfur and gold sensitized and contained apolyethyleneglycol sensitizer as described in Example 2. The pre-bathscontained 1.0 g./ liter of quaternary salt. The cyan D-rnax. and cyanfog for the film strips are given below:

Compound No. Cyan Cyan D-Max Fog C0ntroln0 treatment 3. 80 1. 18Decamethylene bis benzotliiazoliurn perchlorate 2. 90 28 3Ethylbenzothiazolium p-toluene sulfonate- 3. 85 .59 3 l1exyl benzothiazoliurnp-toluene sulfonute 3. 38 .38 3-Nonyl benzothiazolium p-toluenesulfonate, 2. 7a .22 3,3-Trimetliylene bis-(Z-metllyl benzotlnazolium)bromide 2. 84 28 Decamethylene bis (2-methy1 benzothiazolium)perchlorate 3. 12 32 3-(2-Benzothiazolyl 1nethyl)-2-metllylbenzothiazolium p-t01uene sulfonate 3.18 23 2-Methy1-B-naphthothaizoliummethyl p-toluene sulfonate 3. O0 48 Ethylene bis benzothiazoliurnbromide 3. 65 48 Pentamethylene bis benzothiazolium percl1lorate 3.16 l7Hexamethylene bis benzothiazolium perchlorate"- 3. 20 .24 Heptamethylenebis benzothiazolium perchlorate- 3. 21 .28 Nonamethylene bisbenzothiazoliurn perchlorate 3. 23 .32Hexaeosane-l,26-bis-benzothiazoliurn perchlorate" 3.20 .46

As evident from the above data, our invention is concerned primarilywith treatment of the ordinarily employed gelatino-silver-halidedeveloping-out emulsions. While the examples are concerned primarilywith silver bromiodide emulsions, it is to be understood that othersilver halide emulsions can be employed, such as silver chloride,4chlorobromide, -chloroiodide, -chlorobrom iodide and -bromidedeveloping-out emulsions. These emulsions can be coated in the usualmanner on any support, such as glass, cellulose nitrate film, celluloseacetate film, polyvinylacetyl resin film, etc.

The emulsions can be chemically sensitized by any of the acceptedprocedures. The emulsions can be digested with naturally active gelatin,or sulfur compounds can be added such as those described in SheppardU.S. Patent 1,574,944, issued March 2, 1926, Sheppard et al. U.S. Patent1,623,499, issued April 5, 1927, and Sheppard et a l. U.S Patent2,410,689, issued November 5, 1946.

The emulsions can also be treated with salts of the noble metals such asruthenium, rhodium, palladium, iridium, and platinum. Representativecompounds are ammonium chloropalladate, potassium chloroplatinate, andsodium chloropaladite, which are used for sensitizing in amounts belowthat which produces any substantial fog inhibition, as described inSmith and Trivelli U.S. Patent 2,448,060, issued August 31, 1948, and asanti-foggants in higher amounts, as described in Trivelli and Smith U.S.Patents 2,566,245, issued August 28, 1951, and 2,566,263, issued August28, 1951.

The emulsions can also be chemically sensitized with gold salts asdescribed in Waller et al. U.S. Patent 2,399,- 083, issued April 23,1946, or stabilized with gold salts as described in Damsehroder U.S.Patent 2,597,856, issued May 27, 1952, and Yutzy and Leermakers U.S.Patent 2,597,915, issued May 27, 1952. Suitable compounds are potassiumchloroaurite, potassium aurithiocyanate, potassium chloroaurate, aurictrichloride and Z-aurosulfobenzothiazole methochloride.

The emulsions can also be chemically sensitized with reducing agentssuch as stannous salts (Carroll U.S. Patent 2,487,850, issued November15, 1949), polyamines, such as diethyl triamine (Lowe and Jones U.S.Patent 2,518,698, issued August 15, 1950), polyamines, such as spermine(Lowe and Allen U.S. Patent 2,521,925, issued September 12, 1950), orbis([i-aminoethyl) sulfide and its water-soluble salts (Lowe and JonesU.S. Patent 2,521,- 926, issued September 12, 1950).

The emulsions can also be optically sensitized with cyanine andmerocyanine dyes, such as those described in Brooker U.S. Patents1,846,301, issued February 23, 1932; 1,846,302, issued February 23,1932; and 1,942,- 854, issued January 9, 1934; White U.S. Patent1,990,507, issued February 12, 1935; Brooker and White U.S. Patents2,112,140, issued March 22, 1938; 2,165,338, issued July 11, 1939;2,493,747, issued January 10, 1950, and 2,739,964, issued March 27,1956; Brooker and Keyes U.S. Patent 2,493,748, issued January 10, 1950;Sprague U.S. Patents 2,503,776, issued April 11, 1950, and 2,519,-

001, issued August 15, 1950; Heseltine and Brooker U.S.

Patent 2,666,761, issued January 19, 1954; Heseltine U.S.

Patent 2,734,900, issued February 14, 1956; Van Lare U.S.. Patent2,739,149, issued March 20, 1956; and Kodak Limited British Patent450,958, accepted July 15, 1936.

The emulsions can also be stabilized with the mercury compounds ofAllen, Byers and Murray U.S. Patent 2,728,663, issued December 27, 1955;Carroll and Murray U.S. Patent 2,728,664, issued December 27, 1955; andLeubner and Murray U.S. Patent 2,728,665, issued December 27, 1955; thetriazoles of Heimbach and Kelly U.S. Patent 2,444,608, issued July 6,1948; the azaindenes of Heimbach and Kelly U.S. Patents 2,444,605 and2,444,- 606, issued July 6, 1948; Heirnbach U.S. Patents 2,444,- 607,issued July 6, 1948, and 2,450,397, issued September 28, 1948;l-ieimbach and Clark U.S. Patent 2,444,609, issued July 6, 1958; Allenand Reynolds U.S. Patents 2,713; 541, issued July 19, 1955, and2,743,181, issued April 24, 1956; Carroll and Beach U.S. Patent2,716,062, issued August 23, 1955; Allen and Beilfuss U.S. Patent2,735,- 769, issued February 21, 1956; Reynolds and Sagal U.S. Patent2,756,147, issued July 24, 1956; Allen and Sagura U.S. Patent 2,772,164,issued November 27, 1956, and those disclosed by Birr in Z. wiss. Phot,vol. 47, 1952, pages 2 28; the disulfides of Kodak Belgian Patent 569,-317, issued July 31, 8; the quaternary benzothiazolium compounds ofBrooker and Stand U.S. Patent 2,131,038, issued September 27, 1938, orthe polymethylene bisbenzothiazolium salts of Allen and Wilson U.S.Patent 1 1 2,694,716, issued November 16, 1954; or the zinc and cadmiumsalts of Jones U.S. Patent 2,839,405, issued June17,1958.

The emulsions may also contain speed-increasing compounds of thequaternary ammonium type of Carroll U.S. Patent 2,271,623, issuedFebruary 3, 1942; Carroll and Allen U.S. Patent 2,288,226, issued June30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued November23, 1943; and the polyethyleneglycol type of Carroll and Beach U.S.Patent 2,708,162, issued May 10, 1955.

The emulsions may contain a suitable gelatin plasticizer such asglycerin; a dihydroxy alkane such as 1,5-pentane diol as described inMilton and Murry U.S. application Serial No. 588,951, filed June 4,1956; an ester of an ethylene bis-glycolic acid such as ethylenebis(methyl glycolate) as described in Milton U.S. application Serial No.662,564, filed May 31, 1957; bis-(ethoxy diethylene glycol) succinate asdescribed in Gray U.S. application Serial No. 604,333, filed August 16,1956, or a polymeric hydrosol as results from the emulsionpolymerization of a mixture of an amide of an acid of the acrylic acidseries, and acrylic acid ester and a styrene-type compound as describedin Tong U.S. Patent 2,852,386, issued September 16, 1958. Theplasticizer may be added to the emulsion before or after the addition ofa sensitizing dye, if used.

The emulsions may be hardened with any suitable hardener for gelatinsuch as formaldehyde; a halogen-substituted aliphatic acid such asmucobromic acid as described in White U.S. Patent 2,080,019, issued May11, 1937; a compound having a plurality of acid anhydride groups such as7,8-diphenylbicyclo (2,2,2)-7-octene-2,3,5,6-tetracarboxylicdianhydride, or a dicarboxylic or a disulfonic acid chloride such asterephthaloyl chloride or naphthalene-1,5-disulfonyl chloride asdescribed in Allen and Carroll U.S. Patents 2,725,294, and 2,725,295,both issued November 29, 1955; a cyclic 1,2-diketone such ascyclopentane-1,2-dione as described in Allen and Byers U.S. Patent2,725,305, issued November 29, 1955; a bisester of methane-sulfonic acidsuch as 1,2-di-(methane-sulfonoxy)-ethane as described in Allen andLaakso U.S. Patent 2,726,162, issued December 6, 19551,3-dihydr0xymethylbenzimidazol-Z-one as described in July, Knott andP01- lak U.S. Patent 2,732,316, issued January 24, 1956; a dialdehyde ora sodium bisulfite derivative thereof, the aldehyde groups of which areseparated by 2-3 carbon atoms, such as ,B-methyl glutaraldehydebis-sodium bisulfite as described in Allen and Burness U.S. Patentapplication Serial No. 556,031, filed December 29, 1955; a bis-aziridinecarboxamide such as trimethylene bis(1- aziridine carboxamide) asdescribed in Allen and Webster U.S. Patent application Serial No.599,891, filed July 25, 1956; or 2,3-dihydroxy dioxane as described inJeifreys U.S. Patent 2,870,013, issued January 20, 1959.

The emulsions may contain a coating aid such as saponin; a lauryl oroleyl monoether oi polyethyleneglycol as described in Knox and DavisU.S. Patent 2,831,766, issued April 22, 1958; a salt of a sulfated andalkylated polyethyleneglycol ether as described in Knox and Davis U.S.Patent 2,719,087, issued September 27, 1955; an acylated alkyl taurinesuch as the sodium salt of N-oleoyl-N-methyl taurine as described inKnox, Twardokus and Davis U.S. Patent 2,739,891, issued March 27, 1956;the reaction product of a dianhydride of tetracarboxybutane with analcohol or an aliphatic amine containing from 8 to 18 carbon atoms whichis treated with a base, for example, the sodium salt of the monoester oftetracarboxybutane as described in Knox, Stenberg and Wilson U.S. Patent2,843,487, issued July 15, 1958; a water-soluble maleopimarate or amixture of a Water-soluble maleopimarate and a substituted glutamatesalt as described in Knox and Fowler U.S. Patent 2,823,123, issuedFebruary 11, 1958; an alkali metal salt of a substituted amino acid suchas disodium N-(carbop-tert. octylphenoxypentaethoxy)-glutamate asdescribed in Knox and Wilson U.S. patent application Serial No. 600,679,filed July 30, 1956; or a sulfosuccinamate such as tetrasodiumN-(l,2-dicarboxyethyl)- N-octadecyl sulfosuccinamate or N-lauryldisodium sulfosuccinamate as described in Knox and Stenberg U.S. patentapplication Serial No. 691,125, filed October 21, 1957.

in the preparation of the silver halide dispersions employed forpreparing silver halide emulsions, there may be employed as thedispersing agent for the silver halide in its preparation, gelatin orsome other colloidal material such as colloidal albumin, a cellulosederivative, or a synthetic resin, for instance, a polyvinyl compound.Some colloids which may be used are polyvinyl alcohol or a hydrolyzedpolyvinyl acetate as described in Lowe U.S. Patent 2,286,215, issuedJune 16, 1942; a far hydrolyzed cellulose ester such as celluloseacetate hydrolyzed to an acetyl content of 1926% as described in U.S.Patent 2,327,808 of Lowe and Clark, issued August 24, 1943; awater-soluble ethanolamine cellulose acetate as described in Yutzy U.S.Patent 2,322,085, issued June 15, 1943; a polyacrylamide having acombined acrylamide content of 3060% and a specific viscosity of 0.25l.5on an imidized polyacrylamide of like acrylamide content and viscosityas described in Lowe, Minsk and Kenyon U.S. Patent 2,541,474, issuedFebruary 13, 1951; zein as described in Lowe U.S. Patent 2,563,791,issued August 7, 1951; a vinyl alcohol polymer containing urethanecarboxylic acid groups of the type described in Unruh and Smith U.S.Patent 2,768,154, issued October 23, 1956; or containing cyano-acetylgroups such as the vinyl alcohol-vinyl cyanoacetate copolymer asdescribed in Unruh, Smith and Priest U.S. Patent 2,808,331, issuedOctober 1, 1957; or a polymeric material which results from polymerizinga protein or a saturated acylated protein with a monomer having a vinylgroup as described in U.S. Patent 2,852,382, of lllingsworth, Dann andGates, issued September 16, 1958.

If desired, compatible mixtures of two or more of these colloids may beemployed for dispersing the silver halide in its preparation.Combinations of these antifoggants, sensitizers, hardeners, etc., may beused.

The Lowry Red (Wratten No. 92) filter referred to above transmits onlyradiation beyond about 630 m (i.e., absorbs substantially all radiationless. than about 630 Inn).

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be elfected Within the spirit and scope of theinvention as described hereina'oove and as defined in the appendedclaims.

What we claim is:

' 1. A photographic reversal color process for processing a photoexposedmulti-layer photographic element comprising a support and a photographicsilver halide emulsion sensitive to the blue region of the spectrum, aphotographic silver halide emulsion spectrally sensitized to the greenregion of the spectrum and a photographic silver halide emulsionspectrally sensitized to the red region of the spectrum, comprisingdeveloping said photographic element in a photographic developer forproducing at least one black-and-white negative image but no colorimage, subjecting said photographic element to at least one reversalre-exposure, contacting the silver halide emulsion layers of saidphotographic element with an aqueous solution consisting essentially ofwater and at least 0.25 gram per liter of a compound selected from theclass represented by the following general formula:

wherein R represents a member selected from the class consisting of ahydrogen atom and a lower alkyl group, R represents a member selectedfrom the class consisting of a hydrogen atom, an aryl group and anarylenethiazolyl group, D represents the non-metallic atoms necessary tocomplete an aromatic nucleus, X represents an acid radical and nrepresents a positive integer of from 1 to 26 when R represents a memberselected from the class consisting of a hydrogen atom and anarylenethiazolyl group, and n represents a positive integer of from 1 to3 when R represents an aryl group, and developing a color image in saidphotographic element by development in a photographic developer forproducing a colored image and a positive silver image, said colordevelopment being carried out while a color-coupling component isdispersed throughout said silver halide emulsion layers.

2. A photographic reversal color process for processing a photoexposedmulti-layer photographic element comprising a support and at least onephotographic silver halide emulsion layer sensitive to the blue regionof the spectrum, at least one photographic silver halide emulsionspectrally sensitized to the green region of the spectrum and at leastone photographic silver halide emulsion spectrally sensitized to the redregion of the spectrum, comprising developing said photographic elementin a photographic developer for producing only a black-andwhite negativeimage, contacting said silver halide emulsion layers with an aqueoussolution consisting essentially of water and at least 0.25 gram perliter of a compound selected -from the class represented by thefollowing general formula:

when R represents a member selected from the class consisting of ahydrogen atom and an arylenethiazolyl group, and n represents a positiveinteger of from 1 to 3 when R represents an aryl group, subjecting saidpho tographic element to a reversal re-eXposure and producing a colorimage in said photographic element by color development in a colordeveloper, said color development being carried out while a colorcoupling component is dispersed throughout said silver halide emulsionlayers.

3. A photographic reversal color process for processing a photoexposedmulti-layer photographic element comprising a photographic silver halideemulsion sensitive to the blue region of the spectrum, a photographicsilver halide emulsion spectrally sensitized to the green region of thespectrum and a photographic silver halide emulsion spectrally sensitizedto the red region of the spectrum, comprising subjecting saidphoto-graphic element to development in a photographic developer forproducing only a black-and-white negative image, followed by separatereversal re-eXpo-sure and color development for each of said emulsionsin a photographic color developer containing a color forming compoundcapable of coupling with the oxidation products of said photographiccolor developer to produce a colored image complementary to the regionof the spectrum to which each of said photographic silver halideemulsions is sensitive, the photographic silver halide emulsions of saidphotographic element being treated after negative development but beforeany color development with an aqueous solution consisting essentially ofwater and at least 0.25 gram per liter of a compound selected from theclass: represented by the following general formula:

wherein R represents a member selected from the class consisting of ahydrogen atom and a lower alkyl group, R represents a member selectedfrom the class consisting of a hydrogen atom, an aryl group and anarylenethiazolyl group, D represents the non-metallic atoms necessary tocomplete an aromatic nucleus, X represents an acid radical and nrepresents a positive integer of from 1 to 26 when R represents a memberselected from the class consisting of a hydrogen atom and anarylenethiazolyl group, and n represents a positive integer of from 1 to3 when R represents an aryl group.

4. A photographic reversal color process for processing a photoexposedmulti-layer photographic element comprising a photographic silver halideemulsion sensitive to the blue region of the spectrum, a photographicsilver halide emulsion spectrally sensitized to the green region of thespectrum and a photographic silver halide emulsion spectrally sensitizedto the red region of the spectrum, comprising subjecting saidphotographic element to development in a photographic developer forproducing only a blacl -and-white negative image, followed by separatereversal re-exposure and color development for each of said emulsions ina photographic color developer containing a color forming compoundcapable of coupling with the oxidation products of said photographiccolor developer to produce a colored image complementary to the regionof the spectrum to which each of said photographic silver halideemulsions is sensitive, the photographic silver halide emulsions of saidphotographic element being treated after negative development but betimeany color development with an aqueous solution consisting essentially ofwater and at least 025 gram per liter of a compound selected from thoserepresented by the following general formula:

wherein R represents a member selected from the class consisting of ahydrogen atom and a lower alkyl group, R represents an aryl group, Drepresents the non-metallic atoms necessary to complete an aromaticnucleus, X represents an acid radical and n represents a positiveinteger of from 1 to 3.

5. A photographic reversal color process for processing a photoexposedmulti-layer photographic element comprising a photographic silver halideemulsion sensitive to the blue region of the spectrum, a photographicsilver halide emulsion spectrally sensitized to the green region of thespectrum and a photographic silver halide emulsion spectrally sensitizedto the red region of the spectrum, comprising subjecting saidphotographic element to development in a photographic developer forproducing only a black-and-white negative image, followed by separatereversal re-eXposure and color development for each of said emulsions ina photographic color developer containing a color-forming compoundcapable of coupling with the oxidation products of said photographiccolor developer to produce a colored image complementary to the regionof the spectrum to which wherein R represents a member selected from theclass consisting of a hydrogen atom and a lower alkyl group, Rrepresents a hydrogen atom, D represents the nonmetallic atoms necessaryto complete an aromatic nucleus, X represents an acid radical and nrepresents a positive integer of from 1 to 26.

6. A photographic reversal color process for processing a photoexposedmulti-layer photographic element comprising a photographic silver halideemulsion sensitive to the blue region of the spectrum, a photographicsilver halide emulsion spectrally sensitized to the green region of thespectrum and a photographic silver halide emulsion spectrally sensitizedto the red region of the spectrum, comprising subjecting saidphotographic element to development in a photographic developer forproducing only a black-and-white negative image, following by separatereversal re-exposure and color development for each of said emulsions ina photographic color developer containing a color-forming compoundcapable of coupling 'with the oxidation products of said photographiccolor developer to produce a colored image complementary to the regionof the spectrum to which each of said photographic silver halideemulsions is sensitive, the photographic silver halide emulsions of saidphotographic element being treated after negative development but beforeany color development with an aqueous solution consisting essentially ofwater and at least 0.25 gram per liter of a compound selected from theclass represented by the following general formula:

wherein R represents a member selected from the class consisting of ahydrogen atom and a lower alkyl group, 1) represents the non-metallicatoms necessary to complete an aromatic nucleus, X represents an acidradical, and m represents a positive integer of from 1 to 26.

7. A photographic reversal color process for processing a photoexposedmulti-layer photographic element comprising a photographic silver halideemulsion substantially sensitive only to the blue region of the visiblespectrum, a photographic silver halide emulsion spectrally sensitized tothe green region of the visible spectrum and a photographic silverhalide emulsion spectrally sensitized to the red region of the visiblespectrum, comprising subjecting said photographic element to developmentin a photographic developer for producing only a black-and- Whitenegative image, exposing the red sensitive emulsion of said photographicelement to red radiation, developing said red sensitive silver halideemulsion in a color developer containing a col-or forming compoundcapable of coupling with the oxidation products of the color developingagent of said photographic color developer to produce a cyan image, thephotographic silver halide emulsion spectrally sensitized to the redregion of the visible spectrum being treated after negative develop- 16ment but before any color development with an aqueous solutionconsisting essentially of Water and at least 0.25 gram per liter of acompound selected from the class represented by the following generalformula:

wherein R represents a member selected from the class consisting of ahydrogen atom and a lower alkyl group, R represents an aryl group, Drepresents the non-metallic atoms necessary to complete an aromaticnucleus, X represents an acid radical and n represents a positiveinteger of from 1 to 3, said photographic element being washed withwater after treatment in said aqueous solution, and after production ofsaid cyan image in said red-sensitized silver halide emulsion layer,exposing said blue sensitive silver halide emulsion layer to blue lightand developing said blue sensitive silver halide emulsion in aphotographic color developer for producing a yellow image in said bluesensitive silver halide emulsion layer, fogging the unexposed silverhalide in said green-sensitized silver halide emulsion layer anddeveloping said green-sensitized silver halide emulsion layer in aphotographic color developer for producing a magenta image, thecolor-forming compounds for producing the respective yellow and magentaimages being incorporated in the respective color developer-s.

8. A photographic reversal color process for processing a photoexposedmulti-layer photographic element comprising a photographic silver halideemulsion substantially sensitive only to the blue region of the visiblespectrum, a photographic silver halide emulsion spectrally sensitized tothe green region of the visible spectrum and a photographic silverhalide emulsion spectrally sensitized to the red region of the visiblespectrum, comprising subjecting said photographic element to developmentin a photographic developer for producing only a black-andlwhitenegative image, exposing the red sensitive emulsion of said photographicelement to red radiation, developing said red sensitive silver halideemulsion in a color developer containing a color-forming compoundcapable of coupling with the oxidation products of the color developingagent of said photographic color developer to produce a cyan image, thephotographic silver halide emulsion spectrally sensitized to the redregion of the visible spectrum being treated after negative developmentbut before any color development with an aqueous solution consistiongessentially of water and at least 0.25 gram per liter of a compoundselected from the class represented by the following general formula:

wherein R represents a member selected from the class consisting of ahydrogen atom and a lower alkyl group, R represents a hydrogen atom, Drepresents the nonrnetallic atoms necessary to complete an aromaticnucleus, X represents an acid radical and n represents a positiveinteger of from 1 to 26, said photographic element being washed withwater after treatment in said aqueous solution, and after production ofsaid cyan image :in said redsensitized silver halide emulsion layer,exposing said blue sensitive silver halide emulsion layer to blue lightand developing said blue sensitive silver halide emulsion in aphotographic color developer for producing a yellow image in said bluesensitive silver halide emulsion layer, fogging the unexposed silverhalide in said green-sensitized silver halide emulsion layer anddeveloping said green sensitized silver halide emulsion layer in aphotographic color developer for producing a magenta image, thecolorforrning compounds for producing the respective yellow and magentaimages being incorporated in the respective color developers.

9. A photographic reversal color process for processing a photoex-posedmulti-layer photographic element comprising a photographic silver halideemulsion substantially sensitive only to the blue region of the visiblespectrum, a photographic silver halide emulsion spectrally sensitized tothe green region of the visible spectrum and a photographic silverhalide emulsion spectrally sensitized to the red region of the visiblespectrum, comprising subjecting said photographic element to developmentin a photographic developer for producing only a black-andwhite negativeimage, exposing the red sensitive emulsion of said photographic elementto red radiation, developing said red sensitive silver halide emulsionin a color developer containing a color-forming compound capable ofcoupling with the oxidation products of the color developing agent ofsaid photographic color developer to produce a cyan image, thephotographic silver halide emulsion spectrally sensitized to the redregion of the visible spectrum being treated after negative develop mentbut before any color development with an aqueous solution consistingessentially of water and at least 0.25 gram per liter of a compoundselected from the class represented by the following general formula 13wherein R represents a member selected from the class consisting of ahydrogen atom and a lower :alkyl group, D represents the non-metallicatoms necessary to complete an aromatic nucleus, X represents an acidradical and m represents a positive integer of from 1 to 26.

10. A process according to claim 9 wherein said aqueous solutioncontains decamethylene-bis-benzothiazolium perchlorate.

11. A process according to claim 8 wherein said aqueous solutioncontains 3-ethylbenzothiazolium-p-toluenesulfonate.

12. A process according to claim 9 wherein said aqueous solutioncontains3-(2-benzothiazolylrnethyl)-2-methylb-enzothiazolium-p-toluenesulfonate.

13. A process according to claim 9 wherein said aqueous solutioncontains pentamethylene-bis-2-methylbenzothiazolium perchlorate.

14. A process according to claim 9 wherein said aqueous solutioncontains heXamethylene-bisbenzothiazolium perchlorate.

References Cited in the file of this patent UNITED STATES PATENTS2,356,486 Weissberger et al. Aug. 22, 1944 2,376,141 Henri et al. May15, 1945 2,384,663 Weissberger et al. Sept. 11, 1945 2,648,604 Welliveret al. Aug. 11, 1953 2,694,716 Allen et al Nov. 16, 1954 2,899,306 SpathAug. 11, 1959

1. A PHOTOGRAPHIC REVERSAL COLOR PROCESS FOR PROCESSING A PHOTOEXPOSEDMULTI-LAYER PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT AND A PHOTOGRAPHICSILVER HALIDE EMULSION SENSITIVE TO THE BLUE REGION OF THE SPECTRUM, APHOTOGRAPHIC SILVER HALIDE EMULSION SPECTRALLY SENSITIZED TO THE GREENREGION OF THE SPECTRUM AND A PHOTOGRAPHIC SILVER HALIDE EMULAIONSPECTRALLY SENSITIZED TO THE RED REGION OF THE SPECTRUM, COMPRISINGDEVELOPING SAID PHOTOGRAPHIC ELEMENT IN A PHOTOGRAPHIC DEVELOPER FORPRODUCING AT LEAST ONE BLACK-AND-WHITE NEGATIVE IMAGE BUT NO COLORIMAGE, SUBJECTING SAID PHOTOGRAPHIC ELEMENT TO AT LEAST ONE REVERSALRE-EXPOSURE, CONTACTING THE SILVER HALIDE EMULSION LAYERS OF SAIDPHOTOGRAPHIC ELEMENT WITH AN AQUEOUS SOLUTION CONSISTNG ESSENTIALLY OFWATER AND AT LEAST 0.25 GRAM PER LITER OF A COMPOUND SELECTED FROM THECLASS REPRESENTED BY THE FOLLOWING GENERAL FORMULA: